201212056 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種永久磁石及永久磁石之製造方法。 【先前技術】 近年來，對於油電混合車或硬碟驅動器等中使用之永久 磁石電動機而言，要求小型輕量化、高輸出化及冑效率化。 而且，於上述永久磁石電動機實現小型輕量化、高輸出化 及高效率化時，對埋設於永久磁石電動機中之永久磁石而 言，要求磁特性之進一步提高。再者，作為永久磁石，有 鐵氧體磁石、Sm-Co系磁石、Nd-Fe-B系磁石、8〇121^丨7队 系磁石等，尤其係彡留磁通密度較高之Nd_Fe_B系磁石適於 作為永久磁石電動機用之永久磁石。 於此’作為永久磁石之製造方法’通常係使用粉末燒結 法。於此，粉末燒結法係首先將原材料進行粗粉碎，並利 用喷射磨機（乾式粉碎）或濕式珠磨機（濕式粉碎）製造已微 粉碎之磁石粉末《其後’將該磁石粉末放入模具一面自 外部施加磁場，-面擠壓成形為所需之形狀。繼而，將成 形為所需形狀之固形狀之磁石粉末以特定溫度（例如201212056 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method of manufacturing a permanent magnet and a permanent magnet. [Prior Art] In recent years, permanent magnet motors used in hybrid electric vehicles, hard disk drives, and the like are required to be small, lightweight, high in output, and high in efficiency. Further, when the permanent magnet motor is reduced in size, weight, output, and efficiency, it is required to further improve the magnetic characteristics of the permanent magnet embedded in the permanent magnet motor. Further, as permanent magnets, there are ferrite magnets, Sm-Co magnets, Nd-Fe-B magnets, 8〇121^丨7 team magnets, etc., especially Nd_Fe_B systems with high magnetic flux density. The magnet is suitable as a permanent magnet for permanent magnet motors. Here, as a method of producing a permanent magnet, a powder sintering method is usually used. Here, the powder sintering method firstly coarsely pulverizes the raw material, and manufactures the finely pulverized magnet powder by a jet mill (dry pulverization) or a wet bead mill (wet pulverization), and then the magnet powder is placed. A magnetic field is applied from the outside to the side of the mold, and the surface is extruded into a desired shape. Then, the magnet powder of the solid shape of the desired shape is formed at a specific temperature (for example)
Nd-Fe-B系磁石為〜115〇。〇進行燒結藉此製造永久 磁石。 [先前技術文獻] [專利文獻] [專利文獻旧本專利特開第3298219號公報（第彳頁、第5頁） 【發明内容】 155069.doc 201212056 [發明所欲解決之問題] 又，眾所周知對於永久磁石之磁特性而言，由於磁石之 磁特&係根據單磁賴粒子理論而導出，故若使燒結體之 1㈣變微小’則基本上會提高磁性能。而且，為了使 燒結體之晶體粒徑變微小，需要使燒結前之磁石原料之粒 徑亦微小》 於此，作為粉碎磁石原料時使用之粉碎方法之一的濕式 珠磨粉碎係於容器中填充珠粒（介質）並使其旋轉添加將原 料混合至溶劑而成之漿料，將原料碾碎而使其粉碎之方 法°繼而’藉由進行濕、式珠磨粉碎’可將磁石原料粉碎至 微小之粒徑範圍（例如0J μιη〜5.0 μηι)為止。 然而，於如上述濕式珠磨粉碎般之濕式粉碎中，作為混 入磁石原料之溶劑，使用甲[環己烷、乙酸乙醋、甲醇 等有機溶劑1此，即便於粉碎後進行真空乾燥等而使有 機溶劑揮發’亦會使C含有物殘留於磁石内。而且，瞧 與碳之反應性非常高，故而若燒結步驟中〇含有物殘留到高 溫為止’則會形成碳化物。其結果，存在因所形成之碳化 物而於燒結後之磁石之主相與晶界相之間產生空隙，無法 緻密地燒結磁石整體，使得磁性能顯著下降的問題❶又， 即便於未產生空隙之情形時，亦存在因所形成之碳化物而 於燒結後之磁石之主相内析出aFe，使得磁石特性大幅下降 之問題。 本發明係為解決上述先前之問題點開發而成者其目的 在於提供一種永久磁石及永久磁石之製造方法，將濕式粉 155069.doc 201212056 碎中混入有有機溶劑之磁石粉末在燒結之前於氫氣環境下 進行預燒，藉此可預先減少磁石粒子所含之碳量，其結果， 於燒結後之磁石之主相與晶界相之間不會產生空隙，又， 可緻密地燒結磁石整體。 [解決問題之技術手段] 為達成上述目的，本發明之永久磁石之特徵在於其係藉 由如下步驟製造而成.將磁石原料於有機溶劑中進行濕式 粉碎而獲得磁石粉末；藉由將上述磁石粉末成形而形成成 形體；將上述成形體於氫氣環境下進行預燒而獲得預燒 體；以及對上述預燒體進行燒結。 又，本發明之永久磁石之特徵在於其係藉由如下步驟製 造而成：將磁石原料於有機溶劑中進行濕式粉碎而獲得磁 石粉末；將上述磁石粉末於氫氣環境下進行預燒而獲得預 燒體；藉由將上述預燒體成形而形成成形體；以及對上述 成形體進行燒結。 又，本發明之永久磁石之特徵在於，燒結後所殘存之碳 量為0.1 wt%以下。 又，本發明之永久磁石之製造方法之特徵在於包含如下 步驟：將磁石原料於有機溶劑中進行濕式粉碎而獲得磁石 粉末；藉由將上述磁石粉末成形而形成成形體；將上述成 形體於氫氣環境下進行預燒而獲得預燒體；以及對上述預 燒體進行燒結。 進而’本發明之永久磁石之製造方法之特徵在於包含如 下步驟：將磁石原料於有機溶劑中進行濕式粉碎而獲得磁 155069.doc 201212056 石粉末；將上述磁石粉末於氫氣環境下進行預燒而獲得預 燒體；藉由將上述預燒體成形而形成成形體；以及對上述 成形體進行燒結。 [發明之效果] 根據具有上述構成之本發明之永久磁石將作為永久磁 石之製造步驟之濕式粉碎中混入有有機溶劑之磁石粉末之 成形體在燒結之則於氫氣環境下進行預燒，藉此可預先減 少磁石粒子所含之碳量。其結果，於燒結後之磁石之主相 與晶界相之間不會產生空隙，又，可緻密地燒結磁石整體， 且可防止保磁力下降。又，於燒結後之磁石之主相内不會 析出很多aFe，不會大幅度降低磁石特性。 又，根據本發明之永久磁石，將作為永久磁石之製造步 驟之濕式粉碎中混入有有機溶劑之磁石粉末在燒結之前於 氫氣環境下進行預燒，藉此可預先減少磁石粒子所含之碳 量。其結果’於燒結後之磁石之主相與晶界相之間不會產 生空隙’又，可緻密地燒結磁石整體，且可防止保磁力下 降。又’於燒結後之磁石之主相内不會析出很多aFe，不會 大幅度降低磁石特性。 進而’由於對粉末狀之磁石粒子進行預燒，因此與對成 形後之磁石粒子進行預燒之情形相比，對於磁石粒子整體 而言可更容易進行有機化合物之熱分解。即，可更確實地 減少預燒體中之碳量。 又’根據本發明之永久磁石，由於燒結後所殘存之碳量 為〇. 1 wt°/〇以下，因此於磁石之主相與晶界相之間不會產生 155069.doc • 6 · 201212056 空隙’又’可設為緻密地燒結磁石整體之狀態且可防止 殘留磁通密度下降。又，於燒結後之磁石之主相内不會柝 出很多aFe ’不會大幅度降低磁石特性。 又，根據本發明之永久磁石之製造方法，將濕式粉碎中 混入有有機溶劑之磁石粉末之成形體在燒結之前於氫氣環 境下進行預燒，藉此可預先減少磁石粒子所含之碳量。其 結果，於燒結後之磁石之主相與晶界相之間不會產生空 隙又’可缴推地燒結磁石整體’且可防止保磁力下降。 又，於燒結後之磁石之主相内不會析出很多aFe，不會大幅 度降低磁石特性。 進而’根據本發明之永久磁石之製造方法，將濕式粉碎 中混入有有機溶劑之磁石粉末在燒結之前於氫氣環境下進 行預燒’藉此可預先減少磁石粒子所含之碳量。其結果， 於燒結後之磁石之主相與晶界相之間不會產生空隙，又， 可緻捃地燒結磁石整體’且可防止保磁力下降。又，於燒 結後之磁石之主相内不會析出很多aFe，不會大幅度降低磁 石特性。 進而’由於對粉末狀之磁石粒子進行預燒，因此與對成 形後之磁石粒子進行預燒之情形相比，對於磁石粒子整體 而吕可更容易進行有機化合物之熱分解。即，可更確實地 減少預燒體中之碳量。 【實施方式】 以下，關於本發明之永久磁石及永久磁石之製造方法經 具體化之實施形態’下面參照圖式而進行詳細說明。 155069.doc 201212056 [永久磁石之構成] 首先’對本發明之永久磁石1之構成進行說明。圖1係表 示本發明之永久磁石1之整體圖。再者，圖1所示之永久磁 石1具有圓柱形狀，但永久磁石1之形狀係根據成形時使用 之模腔之形狀而產生變化。 作為本發明之永久磁石1 ’例如使用Nd_Fe_B系磁石。又， 如圖2所示，永久磁石1係作為有助於磁化作用之磁性相之 主相11與非磁性且稀土類元素濃縮而成之低熔點之富Nd相 12共存之合金。圖2係將構成永久磁石磁石粒子放大 表不之圖。 於此，主相11成為作為化學計量組成之Nd2FeMB金屬間 化合物相（Fe之一部分亦可被（：〇取代）佔較高之體積比例之 狀態。另一方面，富Nd相12包含較相同之作為化學計量組 成之Nd2Fe“B(Fe之一部分亦可被c〇取代）相比Ndi組成比 率更多之金屬間化合物相（例如，Nd2 〇~3 〇Fei4B金屬間化合 物相）。又，於富Nd相12中，為提高磁特性，亦可少量含有 Dy ' Tb、Co、Cu、A卜Si等其他元素。 而且，於永久磁石1中，富Nd相12承擔如下所述之作用β 一⑴炫點較低（約600t:)，燒結時成為液相，有助於磁石之 冋密度化、即磁化之提高。（2)消除晶界之凹凸減少逆磁 嘴之新產生點（new ereati()n she)而提高保磁力。⑺將主相 磁性絕緣並增加保磁力。 因此’右燒結後之永久磁石1中之富Nd相12之分散狀態不 良則會導致局部燒結不良、磁性之下降，&而於燒結後 155069.doc 201212056 之永久磁石1中均勻地分散有富^^^相12將變得重要。 又，作為Nd-Fe-B系磁石之製造中產生之問題，可列舉已 燒t之合金中生成aFe之情況。作為原因，可列舉於使用包 含基於化學計量組成之含量之磁石原料合金而製造永久磁 石之情形時，製造過程中稀土類元素與氧或碳結合，導致 稀土類元素相對化學計量組成不夠之狀態。於此，aFe係具 有變形能且未被粉碎而殘存於粉碎機中，故而不僅降低粉 碎合金時之粉碎效率，而且亦對粉碎前後之組成變動、粒 度分佈造成影響。進而，若aFe在燒結後亦殘存於磁石中， 則會導致磁石之磁特性之下降。 而且，上述永久磁石1中之含有Nd2全稀土類元素之含量 較理想的疋較基於上述化學計量組成之含量（26 7 wt%)多 0.1 wt〇/〇〜10.0 wt%、更佳多〇」wt%〜5 〇 wt%之範圍内。具 體而言，將各成分之含量設為如下，即，Nd: 25〜37 wt%， B: 1〜2 Wt%，Fe(電解鐵）：60〜75 wt%e將永久磁石i中之 稀土類元素之含量設為上述範圍’藉此可使富Nd相12均勻 地为散至燒結後之永久磁石1中。又，即便製造過程中稀土 類元素與氧或碳結合，亦不會使稀土類元素相對化學計量 組成不夠’可抑制燒結後之永久磁石1中生成aFe。 再者，於永久磁石1中之稀土類元素之含量少於上述範圍 之情形時，難以形成富Nd相12»又，無法充分抑制aFe之生 成〇另一方面，於永久磁石1中之稀土類元素之組成多於上 述範圍之情形時，保磁力之增加停滯，且導致殘留磁通密 度下降，故不實用。 155069.doc -9· 201212056 又於本發明中，於將磁石原料粉碎成微小粒徑之磁石 私末時’進行將透入至有機溶劑中之磁石原、料於有機溶劑 中進行粉碎之所謂濕式粉碎。然而，若將磁石原料於有機 /合劑中進行濕式粉碎，則即便藉由隨後進行真空乾燥等而 使有機溶劑揮發，亦會使有機溶劑等有機化合物殘留於磁 石内。而且，因Nd與碳之反應性非常高，故而若燒結步驟 中C含有物殘留到高溫為止，則會形成碳化物。其結果存 在因所形成之碳化物而於燒結後之磁石之主相與晶界相 (昌Nd相）之間產生空隙，無法緻密地燒結磁石整體，使得 磁性能顯著下降的問題。然而，於本發明中，在燒結之前 進行下述氫預燒處理，藉此可預先減少磁石粒子所含之碳 量0 又’較理想的是將主相i i之晶體粒徑設為〇· 1 μιη〜5.0 μιη。再者，主相丨丨與富Nd相〗2之構成係可藉由例如 SEM(Scanmng Electron Microscope，掃描式電子顯微鏡）或 TEM(Transmission Electron Microscope，穿透式電子顯微 鏡）或二維原子探針法（3D Atom Probe method)而確認。 又，若富Nd相12中含有Dy或Tb，則Dy或Tb抑制晶界之逆 磁鳴之生成，藉此可提高保磁力。 [永久磁石之製造方法1；] 其次’對本發明之永久磁石1之第1製造方法，使用圖3 進行說明。圖3係表示本發明之永久磁石1之第1製造方法中 之製造步驟之說明圖。 首先，製造包含特定分率之Nd-Fe_B(例如Nd: 32.7 wt%， 155069.doc ιη .1U - s 201212056The Nd-Fe-B system magnet is ~115〇. The crucible is sintered to produce a permanent magnet. [Prior Art Document] [Patent Document] [Patent Document] Japanese Patent Laid-Open No. 3298219 (page 、, page 5) [Summary of the Invention] 155069.doc 201212056 [Problems to be Solved by the Invention] In terms of the magnetic properties of the permanent magnet, since the magnetic characteristics of the magnet are derived from the theory of single magnetic particles, if the sintered body 1 (four) is made smaller, the magnetic properties are substantially improved. Further, in order to make the crystal grain size of the sintered body small, it is necessary to make the particle diameter of the magnet raw material before sintering small. Here, the wet bead mill pulverization which is one of the pulverization methods used for pulverizing the magnet raw material is in the container. Filling the beads (medium) and rotating them to add a slurry obtained by mixing the raw materials into a solvent, crushing the raw materials and pulverizing them, and then pulverizing the magnet raw materials by performing wet-type bead mill pulverization Until a small particle size range (for example, 0J μιη to 5.0 μηι). However, in the wet pulverization as in the wet bead mill pulverization, as the solvent to be mixed with the magnet raw material, an organic solvent such as cyclohexane, ethyl acetate or methanol is used, and even after pulverization, vacuum drying or the like is performed. The volatilization of the organic solvent also causes the C content to remain in the magnet. Further, since the reactivity of ruthenium with carbon is extremely high, carbides are formed when the ruthenium-containing material remains in the high temperature in the sintering step. As a result, there is a problem that a void is formed between the main phase of the magnet after sintering and the grain boundary phase due to the formed carbide, and the entire magnet cannot be densely sintered, so that the magnetic properties are remarkably lowered, that is, the void is not generated. In the case of the above, there is also a problem that aFe is precipitated in the main phase of the magnet after sintering due to the formed carbide, and the magnet characteristics are largely lowered. The present invention has been developed to solve the above problems. The object of the present invention is to provide a method for manufacturing a permanent magnet and a permanent magnet. The wet powder 155069.doc 201212056 is mixed with a magnetic powder of an organic solvent before being sintered in hydrogen. The calcination is carried out in an environment, whereby the amount of carbon contained in the magnet particles can be reduced in advance, and as a result, no voids are formed between the main phase of the magnet and the grain boundary phase after sintering, and the entire magnet can be densely sintered. [Technical means for solving the problem] In order to achieve the above object, the permanent magnet of the present invention is characterized in that it is produced by the following steps: wet-pulverizing a magnet raw material in an organic solvent to obtain a magnet powder; The magnet powder is molded to form a molded body; the molded body is calcined in a hydrogen atmosphere to obtain a calcined body; and the calcined body is sintered. Further, the permanent magnet of the present invention is characterized in that it is produced by wet-pulverizing a magnet raw material in an organic solvent to obtain a magnet powder; and pre-calculating the magnet powder in a hydrogen atmosphere to obtain a pre-process a sintered body; a molded body formed by molding the calcined body; and the formed body is sintered. Further, the permanent magnet of the present invention is characterized in that the amount of carbon remaining after sintering is 0.1 wt% or less. Further, the method for producing a permanent magnet according to the present invention includes the steps of: wet-pulverizing a magnet raw material in an organic solvent to obtain a magnet powder; forming a molded body by molding the magnet powder; and forming the molded body The calcination is carried out in a hydrogen atmosphere to obtain a calcined body; and the calcined body is sintered. Further, the method for producing a permanent magnet according to the present invention includes the steps of: wet-pulverizing a magnet raw material in an organic solvent to obtain a magnetic powder 155069.doc 201212056; and calcining the magnet powder in a hydrogen atmosphere; Obtaining a calcined body; forming a shaped body by molding the calcined body; and sintering the formed body. [Effects of the Invention] According to the permanent magnet of the present invention having the above-described configuration, the molded body of the magnet powder in which the organic solvent is mixed in the wet pulverization as the manufacturing step of the permanent magnet is calcined in a hydrogen atmosphere after being sintered. This can reduce the amount of carbon contained in the magnet particles in advance. As a result, no void is formed between the main phase of the magnet after sintering and the grain boundary phase, and the entire magnet can be densely sintered, and the coercive force can be prevented from decreasing. Further, a large amount of aFe is not precipitated in the main phase of the magnet after sintering, and the magnet characteristics are not greatly reduced. Further, according to the permanent magnet of the present invention, the magnet powder in which the organic solvent is mixed in the wet pulverization as a manufacturing step of the permanent magnet is calcined in a hydrogen atmosphere before sintering, whereby the carbon contained in the magnet particles can be reduced in advance. the amount. As a result, no voids are formed between the main phase of the magnet after sintering and the grain boundary phase. Further, the entire magnet can be densely sintered, and the coercive force can be prevented from decreasing. Further, many aFe are not precipitated in the main phase of the sintered magnet, and the magnet characteristics are not greatly reduced. Further, since the powdery magnet particles are calcined, the thermal decomposition of the organic compound can be more easily performed on the entire magnet particles as compared with the case where the magnet particles after the formation are calcined. Namely, the amount of carbon in the calcined body can be more reliably reduced. Further, according to the permanent magnet of the present invention, since the amount of carbon remaining after sintering is 〇.1 wt°/〇, no 155069.doc • 6 · 201212056 void is generated between the main phase of the magnet and the grain boundary phase. The 'again' can be set to densely sinter the state of the magnet as a whole and can prevent the residual magnetic flux density from decreasing. Further, a large amount of aFe ′ is not generated in the main phase of the magnet after sintering, and the magnet characteristics are not greatly reduced. Further, according to the method for producing a permanent magnet of the present invention, the molded body of the magnet powder in which the organic solvent is mixed in the wet pulverization is calcined in a hydrogen atmosphere before sintering, whereby the amount of carbon contained in the magnet particles can be reduced in advance. . As a result, no void is generated between the main phase of the magnet after sintering and the grain boundary phase, and the entire magnet can be sintered by the push, and the coercive force can be prevented from decreasing. Further, a large amount of aFe is not precipitated in the main phase of the magnet after sintering, and the magnet characteristics are not greatly reduced. Further, according to the method for producing a permanent magnet of the present invention, the magnet powder in which the organic solvent is mixed in the wet pulverization is calcined in a hydrogen atmosphere before sintering, whereby the amount of carbon contained in the magnet particles can be reduced in advance. As a result, no voids are formed between the main phase of the magnet after sintering and the grain boundary phase, and the entire magnet can be sintered in abrupt manner, and the coercive force can be prevented from decreasing. Further, a large amount of aFe is not precipitated in the main phase of the sintered magnet, and the magnet characteristics are not greatly reduced. Further, since the powdery magnet particles are calcined, the thermal decomposition of the organic compound can be more easily performed on the entire magnet particles as compared with the case where the magnet particles after the formation are calcined. Namely, the amount of carbon in the calcined body can be more reliably reduced. [Embodiment] Hereinafter, an embodiment of a method for producing a permanent magnet and a permanent magnet according to the present invention will be described in detail with reference to the drawings. 155069.doc 201212056 [Configuration of Permanent Magnet] First, the configuration of the permanent magnet 1 of the present invention will be described. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a general view showing a permanent magnet 1 of the present invention. Further, the permanent magnet 1 shown in Fig. 1 has a cylindrical shape, but the shape of the permanent magnet 1 varies depending on the shape of the cavity used for forming. As the permanent magnet 1' of the present invention, for example, an Nd_Fe_B-based magnet is used. Further, as shown in Fig. 2, the permanent magnet 1 is an alloy in which a main phase 11 of a magnetic phase contributing to magnetization and a low-melting Nd-rich phase 12 in which nonmagnetic and rare earth elements are concentrated are present. Fig. 2 is a view showing an enlarged view of the magnets constituting the permanent magnet. Here, the main phase 11 is a Nd2FeMB intermetallic compound phase which is a stoichiometric composition (a part of Fe may be replaced by a higher volume ratio of (: 〇). On the other hand, the Nd-rich phase 12 contains the same. As a stoichiometric composition, Nd2Fe "B (one part of Fe can also be replaced by c〇) has an intermetallic compound phase with a larger Ndi composition ratio (for example, Nd2 〇~3 〇Fei4B intermetallic compound phase). In the Nd phase 12, in order to improve the magnetic properties, other elements such as Dy 'Tb, Co, Cu, A, Si, etc. may be contained in a small amount. Moreover, in the permanent magnet 1, the Nd-rich phase 12 assumes the action as described below β (1) The bright point is low (about 600t:), which becomes a liquid phase during sintering, which contributes to the density of the magnet, that is, the increase of magnetization. (2) Eliminating the unevenness of the grain boundary and reducing the new generation point of the reverse magnetic nozzle (new ereati( (7) magnetically insulating the main phase and increasing the coercive force. Therefore, the poor dispersion state of the Nd-rich phase 12 in the permanent magnet 1 after the right sintering results in poor local sintering and a decrease in magnetic properties. & and after sintering 155069.doc 201212056 It is important to uniformly disperse the rich phase 12 in the long magnet 1. Further, as a problem occurring in the production of the Nd-Fe-B-based magnet, aFe is formed in the alloy which has been fired. The reason may be exemplified by the case where a permanent magnet is produced by using a magnet raw material alloy containing a content based on a stoichiometric composition, and a rare earth element is combined with oxygen or carbon in the production process, resulting in a state in which the relative stoichiometric composition of the rare earth element is insufficient. Since aFe has deformation energy and remains in the pulverizer without being pulverized, it not only reduces the pulverization efficiency when the alloy is pulverized, but also affects composition variation and particle size distribution before and after pulverization. Further, if aFe is sintered, Remaining in the magnet causes a decrease in the magnetic properties of the magnet. Moreover, the content of the Nd2 total rare earth element in the permanent magnet 1 is preferably based on the stoichiometric composition (26 7 wt%). 0.1 wt〇/〇~10.0 wt%, more preferably 〇wt%~5 〇wt%. Specifically, the content of each component is set as follows, that is, Nd: 25 to 37 wt%, B : 1 to 2 Wt%, Fe (electrolytic iron): 60 to 75 wt% e, the content of the rare earth element in the permanent magnet i is set to the above range', whereby the Nd-rich phase 12 can be uniformly dispersed to the after sintering In the permanent magnet 1, in addition, even if the rare earth element is combined with oxygen or carbon during the manufacturing process, the relative stoichiometric composition of the rare earth element is not made enough to inhibit the formation of aFe in the permanent magnet 1 after sintering. When the content of the rare earth element in the magnet 1 is less than the above range, it is difficult to form the Nd-rich phase 12», and the formation of aFe cannot be sufficiently suppressed. On the other hand, the composition of the rare earth element in the permanent magnet 1 is more than In the case of the above range, the increase in the coercive force is stagnant, and the residual magnetic flux density is lowered, so that it is not practical. 155069.doc -9· 201212056 In the present invention, when the magnet raw material is pulverized into a magnetite having a small particle diameter, the so-called wet which is pulverized in an organic solvent by the magnet which has penetrated into the organic solvent is carried out. Smash. However, when the magnet raw material is wet-pulverized in the organic/mixture, the organic solvent such as an organic solvent remains in the magnet even if the organic solvent is volatilized by subsequent vacuum drying or the like. Further, since the reactivity of Nd and carbon is extremely high, carbides are formed when the content of C in the sintering step remains at a high temperature. As a result, there is a problem that a void is formed between the main phase of the magnet after sintering and the grain boundary phase (Chang Nd phase) due to the formed carbide, and the entire magnet cannot be densely sintered, so that the magnetic properties are remarkably lowered. However, in the present invention, the following hydrogen calcination treatment is carried out before sintering, whereby the amount of carbon contained in the magnet particles can be reduced in advance. 0. It is preferable to set the crystal grain size of the main phase ii to 〇·1. Ιιη~5.0 μιη. Furthermore, the configuration of the main phase 富 and the rich Nd phase 2 can be performed by, for example, SEM (Scanmng Electron Microscope) or TEM (Transmission Electron Microscope) or a two-dimensional atom probe. Confirmed by the 3D Atom Probe method. Further, when Dy or Tb is contained in the Nd-rich phase 12, Dy or Tb suppresses the generation of the reverse magnetic resonance of the grain boundary, whereby the coercive force can be improved. [Manufacturing Method 1 of Permanent Magnet; Next] The first manufacturing method of the permanent magnet 1 of the present invention will be described with reference to Fig. 3 . Fig. 3 is an explanatory view showing a manufacturing procedure in the first manufacturing method of the permanent magnet 1 of the present invention. First, Nd-Fe_B containing a specific fraction is produced (for example, Nd: 32.7 wt%, 155069.doc ιη .1U - s 201212056
Fe(電解鐵）：65.96 wt%，H.34 wm)之铸键。其後’藉 由捣碎機或粉碎機等而將鎊鍵粗粉碎成·叫左右之大 小。或者’溶解鑄旋，利用薄片連鑄法（strip Casting Method) 製作薄片’利用氫壓碎法進行粗粉化。藉此，獲得粗粉碎 磁石粉末3 1。 接著#由;珠磨機之濕式法而將粗粉碎磁石粉末Μ 微粉碎成特定範圍之粒徑(例如〇1 μηι〜5〇_，並且將磁 石粉末分散至溶劑中’從而製作漿料42。再者，於濕式粉 碎時，相對於磁石粉末〇.5 kg，使用甲苯4kg作為溶劑。 再者’詳細的分散條件為如下。 •分散裝置：珠磨機 •分散介質：氧化鍅珠粒 又粕碎時使用之溶劑係有機溶劑，但對於溶劑之種類 並無特別限制’可使用異丙醇 '乙醇、曱醇等醇類，乙酸 乙酯等酯類，戊烷、己烷等低級烴類，苯、曱苯、二甲苯 等芳香族類，酮類，彼等之混合物等。 八後，將所生成之漿料42於成形之前藉由真空乾燥等事 進行乾燥，取出已乾燥之磁石粉末43。其後，藉由成形 裝置50而將已乾燥之磁石粉末壓粉成形為特定形狀。再 者於壓粕成形時，存在將上述已乾燥之微粉末填充至模 腔之乾式法、以及未將漿料42乾燥而填充至模腔之濕式 法，於本發明中，例示使用乾式法之情形。又，亦可使有 機溶劑於成形後之煅燒階段揮發。 如圖3所示，成形裝置5〇包括圓筒狀之鑄模51、相對於鑄 155069.doc 201212056 模5 1 /σ上下方向滑動之下衝頭52、以及相對於相同之鑄模 &上下方向滑動之上衝頭53，由該等包圍之空間構成模 腔54 〇 又’於成形裝置5G中’將-對磁場產生線圈55、56配置 於模腔54之上下位置’對填充至模腔54之磁石粉末43施加 磁力線。將需施加之磁場設為例如1 MA/m。 繼而，於進行壓粉成形時，首先將已乾燥之磁石粉末43 填充至模腔54。其後，驅動下衝頭52及上衝頭53，對填充 至模腔54之磁石粉末43沿箭頭61方向施加壓力而使其成 形。又，於加壓之同時，對填充至模腔54之磁石粉末43， 藉由磁場產生線圏55、56沿與加壓方向平行之箭頭62方向 施加脈衝磁場。藉此，沿所需之方向定向磁場。再者，定 向磁場之方向係必須考慮對由磁石粉末43成形之永久磁石 1要求之磁場方向而決定。 又，於使用濕式法之情形時’亦可一面對模腔54施加磁 場，一面注入漿料，於注入途中或注入結束後，施加較最 初磁場更強之磁場而進行濕式成形。又，亦可以使施加方 向垂直於加壓方向之方式’配置磁場產生線圈55、56。 其次，於氫氣環境下以200。〇〜900°C 、更佳為以 400°C〜900°C (例如600°C )將藉由壓粉成形所成形之成形體 71保持數小時（例如5小時），藉此進行氫中預燒處理。將預 燒中之氫供給量設為5 L/min。於該氫中預燒處理中，進行 使殘存之有機化合物熱分解而減少預燒體中之碳量之所謂 脫碳（decarbonizing)。又，氫中預燒處理係於使預燒體中之 -12- 155069.docFe (electrolytic iron): 65.96 wt%, H.34 wm) cast bond. Thereafter, the pound key is coarsely pulverized into a size of left and right by a masher or a pulverizer. Alternatively, 'dissolving the spinning and spinning, and forming a sheet by a strip casting method' is coarsely pulverized by a hydrogen crushing method. Thereby, the coarsely pulverized magnet powder 31 was obtained. Then, the coarsely pulverized magnet powder Μ is finely pulverized into a specific range of particle diameters (for example, μ1 μηι 5 to 5〇_, and the magnet powder is dispersed in a solvent) to prepare a slurry 42 by a wet method of a bead mill. Further, in the case of wet pulverization, 4 kg of toluene is used as a solvent with respect to the magnet powder of 〇5 kg. Further, the detailed dispersion conditions are as follows. • Dispersing device: bead mill • dispersion medium: cerium oxide beads The solvent used in the mashing is an organic solvent, but the type of the solvent is not particularly limited. 'Isopropanol' alcohol such as ethanol or decyl alcohol, an ester such as ethyl acetate, or a lower hydrocarbon such as pentane or hexane can be used. An aromatic type such as benzene, toluene or xylene, a ketone, a mixture thereof, etc. After eight, the formed slurry 42 is dried by vacuum drying or the like before the forming, and the dried magnet is taken out. Powder 43. Thereafter, the dried magnet powder is powder-molded into a specific shape by a forming device 50. Further, at the time of press forming, there is a dry method of filling the dried fine powder into a cavity, and The slurry 42 is not dried In the wet method of filling the cavity, in the present invention, the dry method is exemplified. Further, the organic solvent may be volatilized in the calcination stage after the forming. As shown in Fig. 3, the forming apparatus 5 includes a cylindrical shape. The mold 51, relative to the casting 155069.doc 201212056, the mold 5 1 / σ slides the lower punch 52 in the up and down direction, and slides the upper punch 53 in the up and down direction with respect to the same mold & The cavity 54 is further disposed in the forming device 5G to apply a magnetic field line to the magnet powder 43 filled into the cavity 54 by disposing the magnetic field generating coils 55, 56 in the upper and lower positions of the cavity 54. The magnetic field to be applied is set, for example. 1 MA/m. Then, in the case of powder compaction, the dried magnet powder 43 is first filled into the cavity 54. Thereafter, the lower punch 52 and the upper punch 53 are driven to fill the magnet filled into the cavity 54. The powder 43 is formed by applying pressure in the direction of the arrow 61. Further, at the same time as the pressurization, the magnet powder 43 filled into the cavity 54 is generated by the magnetic field generating wires 55, 56 in an arrow 62 parallel to the pressing direction. Apply a pulsed magnetic field in the direction. Directional magnetic field. Furthermore, the direction of the directional magnetic field must be determined in consideration of the direction of the magnetic field required for the permanent magnet 1 formed by the magnet powder 43. Also, in the case of the wet method, it is also possible to face the cavity 54. When a magnetic field is applied, the slurry is injected, and a magnetic field stronger than the initial magnetic field is applied to perform wet molding during the injection or after the injection. Alternatively, the magnetic field generating coil 55 may be disposed such that the application direction is perpendicular to the pressing direction. 56. Next, the formed body 71 formed by powder molding is held for several hours in a hydrogen atmosphere at 200 ° C to 900 ° C, more preferably at 400 ° C to 900 ° C (for example, 600 ° C). (For example, 5 hours), thereby performing a pre-burning treatment in hydrogen. The amount of hydrogen supplied in the calcination was set to 5 L/min. In the hydrogen calcination treatment, so-called decarbonization which thermally decomposes the remaining organic compound to reduce the amount of carbon in the calcined body is performed. Moreover, the calcination treatment in hydrogen is carried out in the calcined body -12-155069.doc
S 201212056 碳量未達G.l wt% '更佳為未達G()5 wt%之條件下進行。藉 此，藉由隨後之燒結處理而可緻密地燒結永久磁石丨整體， 不會降低殘留磁通密度或保磁力。 於此，存在藉由上述氫中預燒處理進行預燒之成形體h 中存在NdH3而容易與氧結合之問題，但於第1製造方法中， 成形體7i係於氫預燒後不與外部氣體相接觸地移至下述煅 燒，故而不需要脫氫步驟。於煅燒中，脫去成形體中之氫。 接著，進行將藉由氫$簡處理特預燒之成形體71進 行燒結之燒結處理。再者，作為成形體71之燒結方法除 -般之真空燒結以外’亦可利用將成形體71加壓之狀離下 進行燒結之加壓燒料。例如，於真线結進行燒結 之情形時，以特定之升溫速度升溫至8〇〇。〇〜1〇8〇。〇左右為 止，並保持2小時左右。此期間成為真空烺燒，但真空度較 佳設為1〇·4 Τ〇ΓΓ以下。其後進行冷卻，並再次以 6〇0°C〜HHHTC進行熱處理2小時。繼而，燒結之結果，製造 永久磁石1。 另方面作為加壓燒結，例如有熱壓燒結、熱均壓 (HIP，Hot IS0Static Pressing)燒結、超高壓合成燒結、、氣體 加壓燒結、放電等離子（SPS，Spark pUsma如加㈣)燒結 等。其中’為抑制燒結時之磁石粒子之晶粒成長並且抑制 燒結後之磁石中產生之_ ’較料利用沿單軸方向加壓 之單軸加壓燒結且藉由通電燒結進行燒結之sps燒結。再 者’於㈣SPS燒結進行燒結之情料，較佳為將加壓值設 為30 MPa，於數PaU下之真空氣體環境下以上升 155069.doc -13· 201212056 至940 C為止，其後保持5分鐘。其後進行冷卻，並再次以 600°C〜1000°C進行熱處理2小時。繼而，燒結之結果，製造 永久磁石1 » [永久磁石之製造方法2] 其次，對本發明之永久磁石1之其他製造方法即第2製造 方法，使用圖4進行說明。圖4係表示本發明之永久磁石i 之第2製造方法中之製造步驟之說明圖。 再者’直至生成聚料42為止之步驟係與使用圖3既已說明 之第1製造方法中之製造步驟相同，因此省略說明。 首先’將所生成之漿料42於成形之前藉由真空乾燥等事 月'J進行乾燥，取出已乾燥之磁石粉末43。其後，於氫氣環 境下以200 C〜900°C、更佳為以4〇〇°c〜900°C (例如600°C )將 已乾燥之磁石粉末43保持數小時（例如5小時），藉此進行氫 中預燒處理。將預燒中之氫供給量設為5 L/min。於該氫中 預燒處理中’進行使殘存之有機化合物熱分解而減少預燒 體中之奴量之所謂脫碳。又，氫中預燒處理係於使預燒體 中之奴量未達0.1 wt%、更佳為未達〇 〇5 wt%之條件下進 行。藉此’藉由隨後之燒結處理而可緻密地燒結永久磁石1 整體，不會降低殘留磁通密度或保磁力。 其次’於真空氣體環境下以2〇〇t 〜6〇〇t、更佳為以 400°C〜600°C1〜3小時保持藉由氫中預燒處理進行預燒之粉 末狀之預燒體82,藉此進行脫氫處理。再者，作為真空度， 較佳設為0.1 Torr以下。 於此’存在於藉由上述氫中預燒處理進行預燒之預燒體 155069.docS 201212056 The amount of carbon does not reach G.l wt% 'More preferably, it is not G() 5 wt%. Thereby, the permanent magnet enthalpy can be densely sintered by the subsequent sintering treatment without deteriorating the residual magnetic flux density or coercive force. Here, there is a problem that NdH3 is preliminarily formed in the hydrogen calcination treatment to easily bond with oxygen. However, in the first production method, the molded body 7i is not externally charged after hydrogen calcination. The gas is moved in contact to the calcination described below, so that no dehydrogenation step is required. In the calcination, the hydrogen in the formed body is removed. Next, a sintering treatment is performed in which the molded body 71 which has been specially calcined by the hydrogen treatment is sintered. Further, as the sintering method of the molded body 71, in addition to the vacuum sintering, the pressurization of the sintered body may be carried out by pressing the molded body 71 downward. For example, in the case where the true wire junction is sintered, the temperature is raised to 8 Torr at a specific temperature increase rate. 〇~1〇8〇. 〇About and around, and keep it for about 2 hours. During this period, it is vacuum-burned, but the degree of vacuum is preferably set to 1 〇·4 Τ〇ΓΓ or less. Thereafter, cooling was carried out, and heat treatment was again carried out at 6 °C to HHHTC for 2 hours. Then, as a result of the sintering, a permanent magnet 1 is produced. On the other hand, as the pressure sintering, there are, for example, hot press sintering, hot isostatic pressing (HIP), ultrahigh pressure synthetic sintering, gas pressure sintering, discharge plasma (SPS, Spark pUsma, etc.) sintering. Here, the sp-sintering is performed by suppressing the grain growth of the magnet particles at the time of sintering and suppressing the occurrence of the sintering in the magnet after sintering by uniaxial pressure sintering which is pressed in the uniaxial direction and sintered by electric conduction sintering. Furthermore, in the case of (4) SPS sintering, it is preferable to set the pressurization value to 30 MPa, and to increase by 155069.doc -13·201212056 to 940 C in a vacuum gas atmosphere under several PaU, and thereafter 5 minutes. Thereafter, the mixture was cooled, and heat treatment was again carried out at 600 ° C to 1000 ° C for 2 hours. Then, as a result of the sintering, the permanent magnet 1 » [manufacturing method 2 of permanent magnet] Next, the second manufacturing method which is another manufacturing method of the permanent magnet 1 of the present invention will be described with reference to Fig. 4 . Fig. 4 is an explanatory view showing a manufacturing procedure in the second manufacturing method of the permanent magnet i of the present invention. Further, the steps up to the generation of the polymer 42 are the same as those in the first manufacturing method described with reference to Fig. 3, and therefore the description thereof will be omitted. First, the produced slurry 42 is dried by vacuum drying or the like before molding, and the dried magnet powder 43 is taken out. Thereafter, the dried magnet powder 43 is held at 200 C to 900 ° C, more preferably 4 ° C to 900 ° C (for example, 600 ° C) under a hydrogen atmosphere for several hours (for example, 5 hours). Thereby, the pre-burning treatment in hydrogen is performed. The amount of hydrogen supplied in the calcination was set to 5 L/min. In the hydrogen calcination treatment, the so-called decarburization in which the residual organic compound is thermally decomposed to reduce the amount of slaves in the calcined body is performed. Further, the calcination treatment in hydrogen is carried out under conditions such that the amount of the unburned body is less than 0.1 wt%, more preferably less than 5 wt%. Thereby, the permanent magnet 1 can be densely sintered by the subsequent sintering treatment without reducing the residual magnetic flux density or coercive force. Next, in a vacuum gas atmosphere, the calcined calcined body is preliminarily calcined by hydrogen calcination at 2 Torr to 6 Torr, more preferably at 400 ° C to 600 ° C for 1 to 3 hours. 82, thereby performing a dehydrogenation treatment. Further, the degree of vacuum is preferably set to 0.1 Torr or less. Here, the calcined body is pre-fired by calcination treatment in the above hydrogen 155069.doc
S •14· 201212056 82中存在NdH3而容易與氧結合之問題β 圖5係將進行氫中預燒處理之灿磁石粉末及未進行氣中 預燒處理之Nd磁石粉末分別暴露於氧濃度7 ppm及氧濃度 66 ppm之氣體環境時，表示相對於暴露時間之磁石粉末内 之氧量的圖。如圖5所示，若將進行氫中預燒處理之磁石粉 末放置於高氧濃度66 ppm之氣體環境，則以約丨〇〇〇 磁石 粉末内之氧量自0.4%上升至〇.8%為.止。又，即便放置於低 氧濃度7 ppm之氣體環境，亦以約5〇〇〇 sec磁石粉末内之氧 量自0.4%相同地上升至〇.8%為止。繼而，若Nd與氧結合， 則成為殘留磁通密度或保磁力下降之原因。 因此，於上述脫氫處理中，將藉由氫中預燒處理所生成 之預燒體82中之NdH3(活性度大）階段性地變成NdH3(活性 度大）-NdH2(活性度小），藉此降低藉由氫中預燒處理而活 化之預燒體82之活性度。藉此，即便於將藉由氫中預燒處 理進行預燒之預燒體82於隨後移動到大氣中之情形時，亦 可防止Nd與氧結合，且不會降低殘留磁通密度或保磁力。 其後，藉由成形裝置50而將進行脫氫處理之粉末狀之預 燒體82壓粉成形為特定形狀。由於成形裝置5〇之詳細情況 與使用圖3既已說明之第i製造方法中之製造步驟相同，因 此省略說明。 其後’進行將已成形之預燒體82進行燒結之燒結處理。 再者，燒結處理係與上述第1製造方法相同地，藉由真空燒 結或加壓燒結等進行。由於燒結條件之詳細内容與既已說 明之第1製造方法中之製造步驟相同，因此省略說明。繼 155069.doc •15· 201212056 而，燒結之結果，製造永久磁石1。 再者’於上述第2製造方法中，由於對粉末狀之磁石粒子 進行氮中預燒處理’因此與對成形後之磁石粒子進行氫中 預燒處理之上述第1製造方法相比，具有對於殘存之磁石粒 子整體而言可更容易進行有機化合物之熱分解之優點。 即，與上述第1製造方法相比，可更確實地減少預燒體中之 碳量。 另一方面，於第1製造方法中，成形體71係於氫預燒後不 與外氣體相接觸地移至煅燒，故而不需要脫氫步驟。因 此，與上述第2製造方法相比，可使製造步驟簡化。其中， &上述第2製造方法中’亦於氫預燒後不與外部氣體相接觸 地進行煅燒之情形時，不需要脫氫步驟。 [實施例] 以下本發明之實施例，—面與比較例進行比較，一 面進行說明。 (實施例） 實施例之斂磁石粉末之合金組成係較基於化學計量组 成之分率（Nd : 26.7 wt% ’叫電解鐵）· 72 3心，b : i 〇 ’目比更提高Nd之比率，例如以心計設為 叫购2.7/65.96/1.34。又，料物«粉料之有機 冷劑使用甲本。又’預燒處理係藉由於氫氣環境下以議t 磁石粉末保持5小時而進行。繼而，將預燒中之 風供、，.°量5又為5 L/min。又，p忐形+ 沾 SPS燒結而進行。再者 H結係藉由 再者將其他步驟設為與上述[永久磁石 155069.doc 201212056 之製造方法2]相同之步驟。 (比較例） ，作為進行濕式粉碎時之有機溶劑，使W苯。又，對濕 式叙碎後之磁石粉末未進行氫中預燒處理而成形。繼而， 對已成形之磁石粉末藉由sps燒結進行燒結。其他條件係盘 實施例相同。 (實施例與比較例之殘碳量之比較討論） 圖6係分別表示實施例與比較例之永久磁石之永久磁石 中殘存碳量[Wt0/〇]之圖。 如圖6所示，可知實施例係與比較例相比可大幅度減少殘 存於磁石粒子中之碳量。尤其是，於實施例中，可將殘存 於磁石粒子中之碳量設為0.05 wt%以下。 又，若將實施例與比較例進行比較，則可知儘管使用相 同之有機溶劑進行濕式粉碎，但進行氫中預燒處理之情形 係與未進行氫中預燒處理之情形相比，可大幅度減少磁石 粒子中之碳量。即，可知能夠進行藉由氫中預燒處理而使 有機化合物熱分解，從而減少預燒體中之碳量的所謂脫 碳。作為其結果，可防止磁石整體之緻密燒結或保磁力之 下降。 (貫施例之永久磁石申之藉由XMA(X-ray MicroAnalyzer·，X 射線微量分析儀）之表面分析結果討論） 對實施例與比較例之永久磁石，利用XMA進行表面分 析。圖7係表示實施例之永久磁石之燒結後之SEM照片及晶 界相之元素分析結果之圖。圖8係表示比較例之永久磁石之 155069.doc 17 201212056 燒結後之SEM照片及晶界相之元素分析結果之圖。 又’若將實施例與比較例之各SEM照片進行比較，則於 殘留碳量為固定量以下（例如〇·1 wt%以下）之實施例中，基 本上由敛磁石之主相（Nc^FeMBp 1及看作白色斑點狀之晶 界相92形成有燒結後之永久磁石。又，雖然少量，但亦形 成有〇^6相。與此相對，於較實施例相比殘留碳量更多之比 較例中，除主相91及晶界相92以外，形成有複數個看作黑 色帶狀之aFe相93。於此，aFe係由於燒結時殘留之碳化物 所產生者。即，因Nd與C之反應性非常高，故而如比較例 般’若燒結步驟中有機化合物中之C含有物殘留到高溫為 止’則形成碳化物《其結果’由於所形成之碳化物而於燒 結後之磁石之主相内析出aFe，大幅度降低磁石特性。 另一方面，於實施例中，如上所述進行氫中預燒處理， 藉此可使有機化合物熱分解而預先燒去（減少碳量）所含之 碳。尤其是，將預燒時之溫度設為2〇〇«>c 〜9〇〇〇c、更佳為設 為400 C〜900°C，藉此可燒去必要量以上之所含碳，可使燒 結後殘存於磁石内之碳量未達〇 j wt%、更佳為未達〇 〇5 wt%。繼而，於殘存於磁石内之碳量未達〇1 wt%之實施例 中’於燒結步驟中幾乎不會形成有碳化物，不存在如比較 例般形成複數個aFe相93之虞。其結果，如圖7所示，可藉 由燒結處理緻密地燒結永久磁石丨整體。又，於燒結後之磁 石之主相内不會析出很多aFe，不會大幅度降低磁石特性。 再者’若未添加醇鹽而進行濕式珠磨，並未進行氫預燒 而進行燒結，則殘存碳係於使用曱苯作為溶劑之情形時成 155069.docS •14· 201212056 82There is a problem of NdH3 being easily combined with oxygen. Fig. 5 shows that the magnet powder for calcination in hydrogen and the Nd magnet powder without calcination in gas are exposed to an oxygen concentration of 7 ppm. And a gas environment having an oxygen concentration of 66 ppm, which is a graph showing the amount of oxygen in the magnet powder with respect to the exposure time. As shown in Fig. 5, if the magnet powder subjected to the pre-burning treatment in hydrogen is placed in a gas atmosphere having a high oxygen concentration of 66 ppm, the amount of oxygen in the magnet powder is increased from 0.4% to 〇.8%. until. Further, even in a gas atmosphere having a low oxygen concentration of 7 ppm, the amount of oxygen in the magnet powder was increased from 0.4% to 〇.8% in about 5 sec. Then, if Nd is combined with oxygen, it causes a decrease in residual magnetic flux density or coercive force. Therefore, in the above-described dehydrogenation treatment, NdH3 (large activity) in the calcined body 82 produced by the calcination treatment in hydrogen is gradually changed to NdH3 (large activity)-NdH2 (small activity). Thereby, the activity of the calcined body 82 activated by the calcination treatment in hydrogen is lowered. Thereby, even when the calcined body 82 which is pre-fired by the pre-firing treatment in hydrogen is subsequently moved to the atmosphere, the bonding of Nd and oxygen can be prevented, and the residual magnetic flux density or coercive force is not lowered. . Thereafter, the powder-shaped calcined body 82 subjected to the dehydrogenation treatment is powder-molded into a specific shape by the molding device 50. Since the details of the forming apparatus 5 are the same as those in the i-th manufacturing method which has been described with reference to Fig. 3, the description thereof will be omitted. Thereafter, a sintering treatment for sintering the formed calcined body 82 is performed. Further, the sintering treatment is carried out by vacuum sintering, pressure sintering or the like in the same manner as in the above first production method. Since the details of the sintering conditions are the same as those in the first manufacturing method described above, the description thereof will be omitted. Following the 155069.doc •15·201212056, as a result of the sintering, a permanent magnet 1 was produced. Further, in the second manufacturing method described above, since the powdery magnet particles are subjected to the pre-baking treatment in the nitrogen, the first manufacturing method is performed in comparison with the above-described first production method in which the magnet particles after molding are subjected to the hydrogen calcination treatment. The remaining magnet particles as a whole are more susceptible to the thermal decomposition of organic compounds. That is, the amount of carbon in the calcined body can be more reliably reduced than in the first production method described above. On the other hand, in the first production method, the molded body 71 is transferred to the calcination without being contacted with the external gas after the calcination of hydrogen, so that the dehydrogenation step is not required. Therefore, the manufacturing steps can be simplified as compared with the second manufacturing method described above. In the case where the second manufacturing method described above is also subjected to calcination without contact with the outside air after the hydrogen calcination, the dehydrogenation step is not required. [Examples] Hereinafter, examples of the present invention will be described in comparison with comparative examples. (Example) The alloy composition of the magnetism-receiving powder of the example is higher than the ratio based on the stoichiometric composition (Nd: 26.7 wt% 'called electrolytic iron) · 72 3 core, b: i 〇' For example, it is set to buy 2.7/65.96/1.34 by heart. In addition, the material «organic refrigerant for powders uses a copy. Further, the pre-firing treatment was carried out by holding the magnet powder for 5 hours in a hydrogen atmosphere. Then, the amount of wind in the pre-burning is 5 L/min. Further, p-shaped + immersed in SPS was sintered. Further, the H-junction is set to the same step as the above-mentioned [Manufacturing Method 2 of Permanent Magnet 155069.doc 201212056]. (Comparative Example) As an organic solvent at the time of wet pulverization, W benzene was used. Further, the magnet powder after wet smashing was not subjected to pre-firing treatment in hydrogen. Then, the formed magnet powder is sintered by sps sintering. The other conditions are the same as in the embodiment. (Comparative Discussion on the Amount of Residual Carbon of the Example and the Comparative Example) Fig. 6 is a view showing the amount of residual carbon [Wt0/〇] in the permanent magnet of the permanent magnet of the example and the comparative example, respectively. As shown in Fig. 6, it is understood that the amount of carbon remaining in the magnet particles can be greatly reduced as compared with the comparative example. In particular, in the examples, the amount of carbon remaining in the magnet particles can be made 0.05 wt% or less. Further, when the examples were compared with the comparative examples, it was found that although wet pulverization was carried out using the same organic solvent, the case of performing the pre-firing treatment in hydrogen was larger than the case where the pre-burning treatment in the hydrogen was not performed. The amplitude reduces the amount of carbon in the magnet particles. That is, it is understood that so-called decarburization which reduces the amount of carbon in the calcined body by thermally decomposing the organic compound by calcination in hydrogen can be performed. As a result, it is possible to prevent the dense sintering or the coercive force of the entire magnet from deteriorating. (Performance of the permanent magnet of the embodiment is discussed by the surface analysis result of XMA (X-ray MicroAnalyzer, X-ray microanalyzer)) For the permanent magnets of the examples and the comparative examples, surface analysis was carried out by XMA. Fig. 7 is a view showing the SEM photograph of the sintered permanent magnet of the example and the results of elemental analysis of the grain boundary phase. Fig. 8 is a view showing the results of elemental analysis of the SEM photograph and the grain boundary phase after sintering of 155069.doc 17 201212056 of the permanent magnet of the comparative example. Further, when the SEM photographs of the examples and the comparative examples are compared, in the embodiment in which the residual carbon amount is a fixed amount or less (for example, 〇·1 wt% or less), the main phase of the magnetism is substantially (Nc^ FeMBp 1 and the grain boundary phase 92, which is regarded as a white spot, form a permanent magnet after sintering. Further, although a small amount is formed, a 〇6 phase is formed. In contrast, the amount of residual carbon is more than that of the embodiment. In the comparative example, in addition to the main phase 91 and the grain boundary phase 92, a plurality of aFe phases 93 which are considered to be black strips are formed. Here, aFe is produced by carbides remaining during sintering. The reactivity with C is very high, so as in the comparative example, 'If the C content in the organic compound remains at a high temperature in the sintering step', a carbide is formed, and the result is a magnet after sintering due to the formed carbide. In the main phase, aFe is precipitated to greatly reduce the magnet characteristics. On the other hand, in the embodiment, the pre-firing treatment in hydrogen is performed as described above, whereby the organic compound can be thermally decomposed and burned in advance (reduced carbon amount). Containing carbon. Especially, it will be burnt The degree is set to 2〇〇«>c to 9〇〇〇c, more preferably 400 C to 900 °C, whereby the carbon contained in the necessary amount or more can be burned, and the residual carbon remains in the magnet after sintering. The amount of carbon is less than wtj wt%, more preferably less than 5 wt%. Then, in the embodiment where the amount of carbon remaining in the magnet is less than 1 wt%, 'the sintering step hardly forms. There is a carbide, and there is no such thing as forming a plurality of aFe phases 93 as in the comparative example. As a result, as shown in Fig. 7, the permanent magnet enthalpy can be densely sintered by sintering treatment, and the main magnet after sintering. In the phase, a lot of aFe is not precipitated, and the magnet characteristics are not greatly reduced. Further, if wet bead milling is performed without adding an alkoxide, and sintering is performed without hydrogen calcination, the residual carbon is used as a base. In the case of solvent, it is 155069.doc
S •18- 201212056 為12000 PPm，於使用環己烷作為溶劑之情形時成為31000 ppm。另-方面，若進行氫預燒則於使用曱苯或環己烧之 情形時，均可將殘存碳量降低至300 ppm左右。 再者，於上述實施例及比較例中，使用[永久磁石之製造 方法2]之纟驟中製造之永久磁叾，但於使用[永久磁石之製 ie方法1]之步驟中製造之永久磁石之情形時，亦可獲得相 同之結果。 如上說明般’於本實施形態之永久磁石1及永久磁石1之 製造方法中，將已粗粉碎之磁石粉末於溶劑中藉由珠磨機 進仃粉碎，其後，於氫氣環境下以20(TC〜900°C將已壓粉成 形之成形體保持數小時，藉此進行氫中預燒處理。接著， 以800 C 1180 C進行锻燒，藉此製造永久磁石丨。藉此即 便於使用有機溶劑而將磁石原料進行濕式粉碎之情形時， 亦可在燒結之前使殘存之有機化合物熱分解而預先燒去 (減少碳量）磁石粒子所含之碳，故而燒結步驟中幾乎不會形 成有碳化物。其結果，於燒結後之磁石之主相與晶界相之 間不會產生空隙，χ，可緻密地燒結磁石整體’且可防止 保磁力下降。X ’於燒結後之磁石之主相内不會析出很多 aFe ’不會大幅度降低磁石特性。 進而，將成形體或磁石粉末進行預燒之步驟係藉由於尤 佳為200°C〜900t、更佳為4〇〇〇c ~9〇〇t之溫度範圍内將成 形體保持特㈣間而進行，因此可燒去必要量以上之磁石 粒子中之所含碳。 其結果，燒結後殘存於磁石之碳量成為〇 lwt%以下 '更 155069.doc -19- 201212056 佳為成為0.05 wt%以下，因此於磁石之主相與晶界相之間 不會產生空隙’又，可設為緻密地燒結磁石整體之狀態， 且可防止殘留磁通密度下降。 又，尤其是第2製造方法中，由於對粉末狀之磁石粒子進 行預燒’因此與對成形後之磁石粒子進行預燒之情形相 比，對於磁石粒子整體而言可更容易進行殘存之有機化合 物之熱分解。即，可更確實地減少預燒體中之碳量。又， 於預燒處理後進行脫氫處理，藉此可降低藉由預燒處理而 活化之預燒體之活性度。藉此，防止隨後磁石粒子與氧結 合’且不會降低殘留磁通密度或保磁力。 再者，當然本發明並不限定於上述實施例，於不脫離本 發明之主旨之範圍内可進行各種改良、變形。 又 又 ，磁石粉末之粉碎條件、混煉條件、預燒條件、脫办 條件、燒結條件等並^限定於域實施例所揭*之條件。 關於脫氫步驟，亦可省略。 再者，於上述實施财，料將❹粉末進行濕式 之手段，使用濕式珠磨機，但亦可使用其他濕式粉碎= 例如，亦可使用Nanomizei^ β 武。 【圖式簡單說明】 圖1係表示本發明之永久磁石之整體圖； 圖2係將本發明之永久磁石之晶界附 ； 衣不之模式 圖3係表示本發明之永久磁石 驟之說明圖； 之第1製造方法令 之製造步 J55069.doc -20- 201212056 圖4係表示本發明之永久磁石之第2製造方法中 驟之說明圖； I造步 圖5係表示進行氫中預燒處理之情形與未進行 之氧量變化之圖； 圖6係表示實施例與比較例 殘存碳量之圖； 之情形時 之永久磁石之永久磁石中之 圖7係表示實施例之永久磁石之燒結後之随照片及主 相與晶界相之元素分析結果之圖；及 圖8係表示比較例之永久磁石夕植 艰石之燒結後之SEM照片及主 相與晶界相之元素分析結果之圖。 【主要元件符號說明】 1 永久磁石 11 主相 12 富Nd相 31 粗粉碎磁石粉末 42 漿料 43 磁石粉末 50 成形裝置 51 鑄模 52 下衝頭 53 上衝頭 54 模腔 55、56 磁場產生線圈 61、62 箭頭 155069.doc •21 _ 201212056 71 成形體 82 預燒體 91 主相 92 晶界相 93 aFe相 D 粒徑 d 厚度 155069.doc -22-S •18- 201212056 is 12000 PPm and becomes 31000 ppm when using cyclohexane as a solvent. On the other hand, if hydrogen calcination is carried out, the residual carbon amount can be reduced to about 300 ppm when using benzene or cyclohexene. Further, in the above-described examples and comparative examples, the permanent magnet produced in the step of [manufacturing method 2 of the permanent magnet] was used, but the permanent magnet manufactured in the step of [manufacturing method 1 of the permanent magnet] was used. In the case of the same, the same result can be obtained. As described above, in the method of manufacturing the permanent magnet 1 and the permanent magnet 1 of the present embodiment, the coarsely pulverized magnet powder is pulverized by a bead mill in a solvent, and thereafter, under a hydrogen atmosphere of 20 ( The preform which has been powder-molded is held at TC to 900 ° C for several hours to carry out a pre-burning treatment in hydrogen. Then, calcination is carried out at 800 C 1180 C to produce a permanent magnetite. When the magnet raw material is wet-pulverized by a solvent, the residual organic compound may be thermally decomposed before sintering to burn off (reduced carbon amount) the carbon contained in the magnet particles, so that almost no sintering step is formed in the sintering step. As a result, no voids are formed between the main phase of the magnet after sintering and the grain boundary phase, and the entire magnet can be densely sintered and the coercive force can be prevented from decreasing. X' is the main magnet after sintering. The phase does not precipitate a lot of aFe' does not significantly reduce the magnet characteristics. Further, the step of calcining the shaped body or the magnet powder is preferably from 200 ° C to 900 t, more preferably 4 〇〇〇 c ~ 9〇〇t temperature Since the molded body is kept in the range of (4), the carbon contained in the magnet particles of the necessary amount or more can be burned off. As a result, the amount of carbon remaining in the magnet after sintering becomes 〇lwt% or less 'more 155069.doc - 19-201212056 Preferably, it is 0.05 wt% or less, so that no void is formed between the main phase of the magnet and the grain boundary phase. Further, it is possible to densely sinter the entire magnet and prevent the residual magnetic flux density from decreasing. Further, in the second manufacturing method, in particular, since the powdery magnet particles are pre-fired, it is easier to carry out the remaining organic magnet particles as compared with the case where the magnet particles after molding are pre-fired. Thermal decomposition of the compound, that is, the amount of carbon in the calcined body can be more reliably reduced. Further, dehydrogenation treatment is performed after the calcination treatment, whereby the activity of the calcined body activated by the calcination treatment can be reduced. Thereby, the subsequent combination of the magnet particles and the oxygen is prevented, and the residual magnetic flux density or the coercive force is not lowered. Further, the present invention is of course not limited to the above embodiments without departing from the gist of the present invention. Various improvements and deformations can be made in the enclosure. Further, the pulverization conditions, kneading conditions, pre-firing conditions, de-off conditions, sintering conditions, and the like of the magnet powder are limited to the conditions disclosed in the domain examples. In addition, in the above-mentioned implementation, the powder is subjected to a wet method, and a wet bead mill is used, but other wet pulverization may be used. For example, Nanomizei^β may also be used. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a general view of a permanent magnet of the present invention; FIG. 2 is a view showing a grain boundary of a permanent magnet of the present invention; FIG. 3 is an explanatory view showing a permanent magnet of the present invention; The manufacturing method of the first manufacturing method is a step J55069.doc -20-201212056. FIG. 4 is a schematic view showing a second manufacturing method of the permanent magnet of the present invention. FIG. 5 shows a pre-burning treatment in hydrogen. Figure 6 is a graph showing the amount of residual carbon in the examples and comparative examples; in the case of the permanent magnet of the permanent magnet, Figure 7 shows the sintering of the permanent magnet of the embodiment. With the photo The main phase and the grain boundary phase of the elemental analysis of the graph; and FIG. 8 represents a permanent magnet based Tokyo explants of Comparative Example FIG difficulties result after sintering of an SEM photograph of the stone and the main phase and the grain boundary phase of elemental analysis. [Main component symbol description] 1 Permanent magnet 11 Main phase 12 Rich Nd phase 31 Coarse crushed magnet powder 42 Slurry 43 Magnet powder 50 Forming device 51 Mold 52 Lower punch 53 Upper punch 54 Cavity 55, 56 Magnetic field generating coil 61 , 62 arrow 155069.doc •21 _ 201212056 71 shaped body 82 calcined body 91 main phase 92 grain boundary phase 93 aFe phase D particle size d thickness 155069.doc -22-